Chromable dyestuffs of the triarylmethane series and process of preparing them



Patented Oct. 18, 1938 UNITED STATES PATENT OFFICE CHROMABLE DYESTUFFSOF THE TRIARYL- METHANE SERIES AND PROCESS OF PRE- PARING THEM WilhelmEckert and Karl Schilling, Frankforton-the-Main-Hochst, Germany,assignors to General Aniline Works, Inc., New York, N. Y., a corporationof Delaware No Drawing. Application March 19, 1937, Serial No. 131,936.In Germany March 2'7, 1936 12 Claims.

The present invention relates to chromable dyestuifs of thetriarylmethane series and to a process of preparing them.

According to the present invention very clear dyestufis of thetriarylmethane series capable of being chromed are made by condensing 1molecular proportion of 5-hydroxy-benzene-1,2,4-tricarboxylic acid or3-hydroxybenzene-1,2,4-tricarboxylic acid (hydroxy-trimellitic acid) orthe equivalent amount of the corresponding anhydride with 2 molecularproportions of a cyclic meta-dihydroxy-compound having a reactivehydrogen atom, for instance, by melting the reagents at a temperaturebetween about 150 C. and about 200 C. The dyestuffs may also be made bycondensing, for instance, by melting at dyestufis may also be chromed insubstance whereby they are transformed into the corresponding chromiumcomplex compounds which dye the fiber from an acid bath very clearshades which possess without after-chroming good fastness properties.

The formation of the dyestufi probably occurs, for instance, as follows:

COOH

' OH OH coon HOOC

a temperature between about 150 C. and about 200 C., one molecularproportion of a benzoylbenzoic acid, which is obtainable by condensingone molecular proportion of one of the said hydroxy-trimellitic acidswith only one molecular proportion of a cyclic meta-dihydroxy compoundhaving a reactive hydrogen atom,

or of a halogenation product of such benzoylbenzoic acid, with one mol.of a cyclic meta-dihydroxycompound having a reactive hydrogen atom. Inthis operation there may be used condensing agents as, for instance,concentrated sulfuric acid or para-toluenesulfonic acid, whereby a lowerreaction temperature, for instance, between about 70 C. and about 140 C.may be applied. The product may be halogenated subsequently.

The new dyestuffs dye animal fibers in an acid bath very clear yellow tored tints; by afterchroming them the properties of fastness areconsiderably enhanced. The dyestuffs are also suitable for chromeprinting on cotton.

The

The dyestuffs, obtainable according to the process of the presentinvention are new. There are, for instance, obtained dyestuifs of thefollowing probable formula:

wherein the nuclei B may contain substituents as, for instance, hydroxy,methoxy, halogen, carboxy or sulfo or a condensed benzene nucleus in thepositions X and wherein one Y represents hydroxy and the other Yhydrogen.

The same dyestufis may be characterized by a quinoide constitution asfollows:

\ R W0 V R r X I C I X X X Y coon wherein the values R, X and Y have theaboveindicated meaning.

It is not known with certainty whether the hydroxy-trimellitic acidsreact in the manner presumed. It is also possible that isomerides of theabove-mentioned compounds are formed having the constitution:

or the corresponding quinoide constitution, wherein the values R, X andY have the aboveindicated meaning, or that the products are mixtures ofisomerides of the said formulae.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto; the parts are by weight:

(1) 21 parts of -hydroxy-1, 2, 4-trimellitic anhydride and 22 parts ofresorcinol are finely triturated and melted together. '7 parts of an-,hydrous zinc chloride are introduced into the mass, while stirring, andthe whole is heated at 180 C. to 190 C. for 4 to 5 hours. During thistime the melt solidifies. The mass is cooled and -finely pulverized andthen digested with 100 parts of hot hydrochloric acid of about 5 percent strength for some time. The undissolved yellow residue is filteredwith suction while hot, dissolved in caustic soda solution, the solutionis filtered and the yellow dyestuff is precipitated from the orange-redfiltrate by means of dilute hydrochloric acid. For further purificationthe dyestuff may be recrystallized from aqueous alcohol. By dissolutionin water with the necessary quantity of sodium bicarbonate andevaporation, the easily soluble orange-red sodium salt is obtained.

The dyestuff dyes animal fibers in an acid bat a very clear yellow tint;its properties of fastness are considerably enhanced by after-chroming.

(2) 39 parts of the yellow dyestufi described in Example 1 are suspendedin 200 parts of glacial acetic acid and a solution of 34 parts ofbromine in 100 parts of glacial acetic acid is added, drop by drop,while stirring. When the bromine has been absorbed, the orange-yellowdyestufi is filtered with suction. washed with a small quantity ofglacial acetic acid and then washed with a large quantity of water untilneutral to Congo paper. The dyestufi may be recrystallized from a largequantity of hot glacial acetic acid or aqueous alcohol. It dyes wool inan acid bath orange-yellow tints the fastness of which is enhanced byafter-chroming.

(3) 39 parts of the dyestufi described in Example 1 are suspended in 200parts of glacial acetic acid and a solution of 68 parts of bromine in100 parts of glacial acetic acid is added drop by drop while stirring.When the bromine has been absorbed, the dyestuff is isolated andpurified as indicated in Example 2. The dyestuff has probably thefollowing constitution:

Br Br 7 HO OH or represents an isomeride thereof or a mixture ofisomerides. It dyes wool in an acid bath a very clear yellowish red tintthe fastness properties of which are considerably enhanced byafter-chroming.

(4) 21 parts of 5-hydroxy-trimellitic anhydride, 31 parts ofbeta-resorcylic acid and 14 parts of anhydrous zinc chloride aretriturated and heated at 180 C. in an oil bath for several hours untilthe melt solidifies. After cooling, the crude prodnot is pulverized andboiled with 200 parts of hydrochloric acid of 5 per cent strength; theundissolved yellow dyestuff is filtered with suction while hot. It isdissolved in dilute sodium carbonate solution, yielding an orange-redsolution with a green fluorescence; the solution is filtered and thedyestuff is precipitated by means of a dilute acid. For furtherpurification the dyestufi may be recrystallized from aqueous alcohol. 4=0 parts of this dyestuff are suspended in 160 parts of alcohol and 64parts of bromine are gradually added at ordinary temperature, whilestirring. After standing for several hours the whole 7 HOOC wherein thenumber and the position of the bromine atom or atoms are unknown.Perhaps it is an isomeride thereof or a mixture of isomerides. Thedyestufi dyes animal fibers in an acid bath very clear yellowish redtints; its fastness properties are considerably enhanced byafter-chrommg.

(5) 28 parts of 4-chloro-resorcinol, 20 parts of 5-hydroxy-trimelliticanhydride and 7 parts of anhydrous zinc chloride are finely trituratedand heated at 180 C. in an oil bath until the melt solidifies, whichoccurs after about 5 hours. The pulverized melt is purified by boilingit with dilute hydrochloric acid, dissolving the undissolved residue indilute caustic soda solution and reprecipitating it. For furtherpurification the precipitate is dissolved by boiling it with bariumhydroxide solution, the solution is filtered and the dyestufi isprecipitated from the filtrate by acidification with dilute hydrochloricacid. The dyestufi dyes wool in an acid bath yellow tints which, byafterchroming, become darker and faster.

(6) 16 parts of 1.3-dihydroxy-naphthalene, 10 parts of5-hydroxy-trimellitic anhydride and 4 parts of anhydrous zinc chlorideare melted to-- gether as described in Example 5. The dyestufi ispurified by boiling it with dilute hydrochloric acid, dissolving theinsoluble residue in 250 parts of bicarbonate solution of 5 per cent.strength, filtering the solution and adding 60 parts of sodium chlorideto the filtrate. After stirring for one hour the resulting darkprecipitate'is filtered with suction and the dyestuff is precipitatedfrom the filtrate by means of dilute hydrochloric acid, washed withwater and dried.

The dyestufi dyes animal fibers in an acid bath brown-red tints; thefastness properties are improved by after-chroming.

('7) 25 parts of pyrogallol, 21 parts of 5-hydroxy-trimellitic anhydrideare melted together at 190 C. to 200 C. for 3 to 4 hours while excludingair. The pulverized melt is recrystallized from aqueous alcohol.

The dyestuff thus obtained has probably the following constitution:

OH OH HO\ 0 /OH (8) 42 parts of the dyestufi obtainable by condensationof 2 molecular proportions of pyrogallol with 1 molecular proportion of5-hydroxy-trimellitic anhydride are suspended in 200 parts of glacialacetic acid.

While quickly stirring, a solution of 32 parts of bromine, in 100 partsof glacial acetic acid, is added drop by drop. After consumption of thebromine the dyestuff is precipitated by means of Water andrecrystallized for purification from acetic acid of 50 per centstrength. It forms a red powder, which dissolves in bicarbonate solutionto a red, and in caustic soda solution to a blue or is an isomeridethereof or a mixture of isomerides. The dyestuff dyes wool in an acidbath wine-red shades. The after-chromed dyeings are violet and possessessentially better fastness properties than the non-chromed dyestufi. 20

(9) 32 parts of 2, 4'-dihydroxy-2-benzoyl-orthohydroxy-carboxy-l-benzoicacid having the following constitution:

HO OH HO H O O o o 7 COOH coon OOOH or a mixture of both isomerides(obtainable by condensation of one molecular proportion of5-hydroxy-benzene-l, 2, 4-tricarboxylic acid with one molecularpro-portion of resorcinolor by treating the dyestuff of Example 1 withabout 80 per cent. of caustic soda solution at about 150 C. for aboutone hour) are melted together with 20 parts of resorcinol for 4 to 5hours at 180 C. The yellow melt is pulverized after cooling anddissolved in dilute caustic soda solution. The solution is heated toboiling and acidified with dilute hydrochloric acid. The yellowprecipitate obtained is filtered with suction after cooling, washeduntil neutral and dried. The dyestufi may be recrystallized, if desired,from aqueous alcohol. On dissolution in dilute alkalies and evaporationof thesolution the easily soluble sodium salt of the 'dyestuff isobtained.

The dyestufi dyes the animal fiberin an acid bath yellow shades. Thefastness properties are essentially enhanced by after-chroming.

Instead of resorcinol there may also be used othermeta-dihydroxy-compounds having a reactive hydrogen atom, as, forinstance, chloro-, bromo-, methyl-resorcinol or resorcinolmono methylether and so on.

(10) By bromination of the dyestufi of Example 9, as indicated inExample 2, a dyestufi is obtained which possesses similar properties asdescribed therein. If the bromination is conducted as described inExample 3, a dyestufi is obtained which dyes wool in an acid bath veryclear yellowish red shades, the fastness properties of which areessentially enhanced by after-chroming.

(11) 32 parts of 2, 4-dihydroxy-2-benzoylorthohydroxy-carboxyl-l-benzoicacid (cp. Ex-

ample 9) and 17 parts of beta-resorcylic acid are introduced into 20parts of concentrated sulfuric acid and heated at 70 C. to C. for 6hours, while stirring. Thereupon the mixture obtained is introduced intoabout parts of water','the solution is saturated by meansof sodiumchloride and the yellow precipitate obtained is filtered with suction.In order to eliminate any unchanged 2, 4'-dihydroxy-2-benzoyl-ortho-hydroxy-carboxyl-benzoic acid from the yellowresidue, it is stirred with about 25 parts of slaked lime and 250 partsof water and boiled again. After cooling the diflicultly soluble calciumsalt of the dyestufi is filtered with suction, washed with water and theyellow dyestuff is freed therefrom by means of dilute acids. With thecondensation there occurs simultaneously sulfonation and the dyestuffpossesses probably the following constitution:

HO OH Uyy OOOH HOaS or is an isomeride thereof or a mixture ofisomerides. The dyestuff dyes W001 in an acid bath yellow shades. Thefastness properties are essentially enhanced by after-chroming.

On after-broming in alcohol or glacial acetic acid there are obtaineddyestuffs the Shades of which turn gradually red pari pas'su with thenumber of bromine atoms absorbed.

(12) 16 parts of 2',4-dihydroxy-2-benzoyl- (ortho hydroxy carboxy)-1-benzoic acid (cp. Example 9) and 7.5 parts of pyrogallol are meltedtogether at 160-170 C. for 4 hours while excluding air and stirring.

The pulverized melt is dissolved in sodium carbonate solution of 5 percent strength and filtered. The red solution is heated to boiling andacidified with dilute hydrochloric acid until the reaction becomesfeebly acid to Congo paper. After standing for several hours theprecipitated dyestufi' is filtered with suction, washed with waterseveral times and dried. The dyestufi dissolves in sodium carbonate orbicarbonate solution to a red, and in dilute caustic soda solution to agreen solution. It dyes wool in an acidbath brown-red shades. Theafter-chromeddyeings show, according to the strength of the dyeing, greyor deeply black shades, the fastness of which is considerably enhancedcompared with the nonchromed dyeings.

(13) 40 parts of 2,4'-dihydroXy-2-benzoyl- (ortho-hydroxy-carboxy) 1benzoic acid (cp. Example 9) and 20 parts of 1,3-dihydroxynaphthaleneare heated at 150 C. to 160 C. for 4 hours. The pulverized melt isdissolved in bicarbonate solution and the solution obtained is boiledfor half-an-hour with about.1 part of animal charcoal. The dyestufi isprecipitated from the hot filtered yellow-red solution with dilutehydrochloric acid. Aftercooling entirely the dyestuff is isolated in theusual-manner. For further purification it may be recrystallized from alarge quantity of glacial acetic acid or dioxane. The dyestufi forms ayellow-red, indistinct crystalline powder. It dissolves in bicarbonatesolution to a yellow-red solution having a yellow, fluorescence. It dyeswool in an acid bath clear golden-yellow shades. The chromed dyeings arebrown. and show enhanced fastness properties. 1

(14) 24:par ts of 2',4'-dihydroxy+2-benzoyl-(orthoj-hydroxycarboXy)-1-benzoic acid (cp. Example 9), 10%.; parts ofphloroglucin and 22 parts of para-toluene-sulfonic acid are heated at C.to C. for 3 to 4 hours. The pulverized melt is stirred With about 100parts'of water and the dyestuff is filtered with suction from thesolution containing toluenesulfonic acid. The dyestuff is dissolved insodium carbonate solution, filtered, the red solution obtained is boiledwith 1 part of animal charcoal, filtered, and the dyestuff isprecipitated from the cooled solution by means of dilute hydrochloricacid.

It dyes wool in an acid bath orange-yellow shades. On after-chromingessentially faster brown dyeings are obtained.

(15) 95 parts of 2,4-dihydroxy-3',Sf-dibromo- 2-benzoyl- (ortho-hydroxycarboxy) 1 benzoic acid, which is obtainable from the bromine-freecompound (cp. Example 9) by bromination in alcohol with the necessaryquantity of bromine, 30'parts of pyrogallol and parts of paratoluenesulfonic acid are melted together at 120 C. to 130 C. for 4.hours whileexcluding air. The cooled pulverized melt is stirred in 1000 parts ofwater and the dyestuff is filtered with suction. The brown-black residueis dissolved in sodium carbonate solution. The solution obtained isfiltered and the dyestufi is precipitated therefrom by means of dilutehydrochloric acid.

For further purification it may be recrystallized I from acetic acid of50 per cent strength. The dyestuff dyes wool in an acid bath. Onafterchroming it becomes blackand the fastness properties are enhanced.

(16) 32 parts of 2,4-dihydroxy-2-benzoyl(ortho-hydroxy-carboxy)-1-benzoic acid and 16 parts of4-chloro-resorcinol are melted together at C. to C. for ivhours. It isfurther worked up as described in the foregoing example. The dyestuffdyes wool in an acid bath orangeyellow tints. The after-chromed dyeingis brown and essentially faster.

We claim:

1. A member of the group consisting of compounds of the generalformulae:

x x HO 1 0 I OH and wherein X represents a member of the groupconsisting of hydrogen, hydroxy, halogen, carboxy and sulfonic acid andone Y represents hydroxy and the other Y hydrogen, and the chromiumcomplex compounds of these compounds.

2. A member of the group consisting of compounds of the generalformulae:

X X HO /OH X C I X X r HOOC I OH and H 0 OH KO O\ Oco HOOC I and HO OH Owherein X represents a member of the group consisting of hydrogen,hydroxy, halcgen, carboxy and sulfonicacid, and the chromium complexcompounds of these-compounds. I

3. Compounds of the general formula:'

Br Br HO O OH Br 'Br HOOC being a dyestuff which dyes wool from an acidbath very clear yellowish red shades, the fastness properties of whichare essentially enhanced by after-chroming.

5. The compound of the formula:

wherein X means that the compound is brominated, being a dyestuff whichdyes the animal fiber from an acid bath clear yellowish red shades, thefastness properties of which are essentially enhanced on after-chroming.

6. The compound of the formula:

OH OH HOOO being a dyestuff which dyes wool from an acid bath redshades, which on after-chroming become violet and possess very goodfastness properties.

'7; The process which comprises causing one mol of a hydroxy-trimelliticanhydride of the formula:

CO-O

X CO

to react with two mols of a cyclic m-dihydroxy compound which contains areactive hydrogen atom, by melting the reagents at a temperature ofbetween about C. and about 200 C.

9. The process which comprises causing one mol of a hydroxy-trimelliticanhydride of the formula:

to react with two mols of a cyclic m-dihydroxy compound which contains areactive hydrogen atom, by melting the reagents at a temperature ofbetween about 150 C. and about 200 0., and brominating the compoundsthus obtained.

10. The process which comprises causing one mol of 5-hydroxy-trimel1iticanhydride of the formula:

HOOC

to react with two mols of resorcin by melting at about 180 C. to aboutC. for about 4 to 5 hours a mixture of the reagents in the presence ofanhydrous zinc chloride, separating the dyestufi thus obtained andbrominating it at room temperature in glacial acetic acid.

11. The process which comprises causing one mol of 5-hydroxy-trimelliticanhydride of the formula:

HOOC

I OH

to react with two mols of beta-resorcylic acid by melting at about 180C. for about 5 hours a mixture of the reagents in the presence ofanhydrous zinc chloride, separating the dyestuff thus obtained andbrominating it at room temperature in alcohol.

12. The process which comprises causing one mol offi-hydroxy-trimellitic anhydride of the formula:

to react with two mols of pyrogallol by melting While excluding air, atabout 190 C. to about 200 C. for about 3 to 4 hours a mixture of thereagents.

WlLHELM ECKERT. KARL SCHILLING.

